This paper describes a solvothermal approach to synthesize CuInS2 quantum dots (QDs) and demonstrates their application as a potential electron accepting material for polymer-based hybrid solar cells, for the first time. The CuInS2 QDs with a size of 2-4 nm are synthesized by the solvothermal method with 4-bromothiophenol (HSPh) as both reduction and capping agents, and characterized by XRD, XPS, TEM, FT-IR, cyclic voltammetry (CV), and absorption and photoluminescence spectra. Results reveal that the CuInS2 QDs result from the solvothermal decomposition of a soluble organic sodium salt as an intermediate precursor formed by simple reactions among CuCl2, InCl3, HSPh and Na2S at room temperature; they have an ionization potential (IP) of -5.8 eV and an electron affinity (EA) of -4.0 eV and can quench effectively the luminescence of poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV). Due to the favorable IP and EA positions with respect to MEH-PPV, the CuInS2 QDs act as an effective electron acceptor for the hybrid solar cells based on MEH-PPV/CuInS2-QDs blends with a wide spectral response extending from 300 to 900 nm, by allowing the efficient charge separation for neutral excited states produced either on the polymer or on the QDs. The MEH-PPV/CuInS2-QDs solar cells exhibit a promising open circuit voltage (V-oc) of 0.62 V under the monochromic illumination of 15.85 mW cm(-2) at 470 nm. The charge transfer processes in the solar cells are also described

For characterization of polymer-based solar cells with vertically aligned ZnO nanorod arrays (ZnO-NAs) by intensity modulated photocurrent spectroscopy (IMPS), a dynamic IMPS model is developed, where the structure-related charge generation and transport dynamics are considered. The model describes the IMPS responses affected by the phase shift φ n (ω) due to the exciton diffusion property (ω 0 ) and the structurerelated device ideality factor N, the electron diffusion coefficient D e , the exciton dissociation rate S, and the device structure (e.g., nanorod length d and interspacing l). The main expectations of the model are confirmed by the experimental data of the polymer/ZnO-NA cells with d ) 180-650 nm, offering mechanistic information on the structure-related charge generation, charge transport, and device performance. The presence of the φ n (ω) makes IMPS response not spiral into the origin and the phase angle in its Bode plot not tend to 90°; the d-dependent direct diffusion (DD) and diffusion-reflection (DF) transport processes are normally involved in the travel of injected electrons to the collection electrode; the incident photon-to-current conversion efficiency (IPCE) and the transit time (τ D ) for DD transport under the influence of DF process reach their peak values at d ≈ 500 nm, and the φ n (ω) effect on electron transport is affected by ω 0 , D e , and S. Satisfactory fittings of measured IMPS responses to the model further reveal that the d dependence of the IPCE or the photocurrent actually originates from the S value governed by d-dependent exciton generation and dissociation; when changing d, a larger number of electrons for DD transport causes a smaller N or a more remarkable φ n (ω) effect; a longer τ D is accompanied by a larger RC effect of the ZnO electrode. Those results clearly suggest that a highly efficient polymer/ZnO-NA device requires d ≈ 500 nm and l ) 5-10 nm, along with a high interfacial exciton dissociation efficiency.